Water-insoluble monoazo dyestuffs and process for preparing them

ABSTRACT

WATER-INSOLUBLE MONOAZO DYESTUFFS OF THE GENERAL FORMULA   1-((2-Y,4-X-PHENYL)-N=N-),2-(R1-CO-NH-),4-(R3-CO-CH2-   CH(-R2)-NH-)BENZENE   WHEREIN X REPRESENTS A NITRO OR NITRILE GROUP, Y REPRESENTS A HYDROGEN A HALOGEN ATOM, OR A NITRO OR NITRILE GROUP, R1 REPRESENTS A LOWER ALKYL OR PHENYL RADICAL, R2 REPRESENTS A METHYL, PHENYL, CHLOROPHENYL, HYDROXYPHENYL OR METHYLENEDIOXYPHENYL RADICAL, AND R3 REPRESENTS A METHYL, PHENYL, HYDROXYPHENYL OR LOWER ALKOXY GROUP, AND A PROCESS FOR PREPARING SAID DYESTUFFS.

United States Patent WATER-INSOLUBLE MONOAZO DYESTUFFS AND PROCESS FORPREPARING THEM Helmut Lindner, Frankfurt am Main, Karl Summer,Konigstein, Tauuus, and Heinz Schmidt, Kel kheim, Taunus, Germany,assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius& Bruning, Frankfurt am Main, Germany, a corporation of Germany NoDrawing. Filed July 18, 1967, Ser. No. 654,086

Claims priority, applicatior; Germany, July 30, 1966,

4 Int. Cl. C07c l07i06; 00% 29/04 US. Cl. 260-2071 6 Claims ABSTRACT OFTHE DISCLOSURE Water-insoluble monoazo dyestulfs of the general formulaThe present invention relates to new water-insoluble monoazo dyestuffsand to a process for preparing them; in particular it relates to newwater-insoluble monoazo dyestufls of the general Formula 1 I1IHCO-R1wherein X represents a nitro or a nitrile group, Y represets a hydrogenor a halogen atom, a nitro or a nitrile group, R represents a loweralkyl or a phenyl radical, R represents a methyl radical or a phenylradical which, if desired may be substituted by a chlorine atom, ahydroxy or a methylenedioxy group and R represents a methyl radical, aphenyl radical which may be substituted by a hydroxy group, or a loweralkoxy group.

It has been found that the new water-insoluble monoazo dyestufis of thegeneral Formula 1 can be obtained by diazotizing aromatic amines of thegeneral formula 2 wherein R R and R have the meaning given above.

As diazo components can be used for example the following amines:

4-nitroani1ine, Z-chloro-4-nitro-aniline, 2-bromo-4-nitroaniline,2,4-dinitro-aniline, 2-cyano-4-aniline, 2-nitro-4-cyano-aniline.

The coupling components used according to the process of the presentinvention can be prepared for example by condensing primary aromaticamines of the general formula 4 I[\IHC 0-R1 wherein R has the meaninggiven above, with keto compounds of the general formula 5 wherein R andR have the meanings given above, and hydrogenating the SchilTs bases soformed to the coupling components of Formula 3. Thus there is obtainedfor example by condensation of 3-amino-acetanilide with acetylacetoneand subsequent hydrogenation of the Schilfs base which has formed, thecoupling component of Formula 6 CH3 NHCHOH2C 04111,

l IHC OCHs (6) Formula 7 R -CH=CHC0R (7) wherein R and R have themeanings given above. Thus, for example, by addition of3-amino-acetanilide to benzalacetophenone of the Formula 8 in a strongalkaline medium, the coupling component of Formula 9 NH-C 0-011 isobtained.

The new water-insoluble monoazo dyestuflfs obtainable according to theprocess of the present invention are valuable dispersion dyestuffs whichcan be further treated in usual manner with dispersing agents to givedyeing preparations. On synthetic fibres, such as cellulose triacetatefibres, cellulose 2 /2 acetate fibres, polyamide and polyurethanefibres, but especially on polyester fibres, such as polyethyleneterephthalate fibres, these dyeing preparations yield, at a very goodbuilding up, dyeings and prints having a high tinctorial strength andexcellent fastness to light, thermofixation and wet processing. Inaddition, the dyestuffs prove considerably insensitive to agents havingalkaline action.

For dyeing material of polyester fibres, it is suitable to apply the newdyestufis in the form of the afore-mentioned dyeing preparations in anaqueous suspension at temperatures above C. and under pressure, or at atemperature of about 100 C. With addition of the usual carriers.Furthermore intense dyeings are obtained by impregnating fabrics andhosieries made of polyester materials with a suspension of the newdyestuffs, drying the treated goods and then submitting them for a shortperiod to the action of heat, for example at 190 to 210 C. The dyestuffsare very appropriate for dyeing mixed fibrous materials containingpolyester portions, for example mixtures of polyester fibres with woolor cotton. When dyeing a polyester-wool mixture the wool portion obtainsa weak coloration whereas the polyester portion gives a good yield ofdyestutf being fixed. The wool coloration can easily be removed by anafter-treatment with reducing agents or with emulsifiers.

Coupling components of Formula 3, wherein R represents a phenyl radical,R represents a methyl group and R, a lower alkoxy group, such forexample, as in the coupling component of Formula 10 I IHC OC5H5 given,when coupled with diazonium salts of amines of Formula 2, dispersiondyestulfs that can be further treated in usual manner with dispersingagents to obtain dyeing preparation which, on polyamide and polyurethanefibres, give intense dyeings that have good fastness to light, excellentfastness to wet processing and good :Eastness to fixation.

In comparison to the dyestuffs of next comparable structure which areknown from the French Pat. No. 1,413,474, those of the present inventionare distingushed by a better fastness to light.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the part being by weight unlessotherwise stated.

EXAMPLE 1 18.3 parts of 2.4-dinitro-aniline are introduced into amixture consisting of 70 parts of concentrated sulfuric acid and 31 partof nitrosyl sulfuric acid of 41% strength at 20 C., and the batch isstirred at room temperature for 1 hour. Then a specimen of the dilutedreaction mixture is to show still a small excess of nitrous acid.Subsequently, the diazonium salt solution obtained is poured on 250parts of ice and it is filtered.

23.4 parts of a coupling componentobtained by condensation of3-aminoacetanilide and acetylacetone and subsequent hydrogenation of theSchiffs base formedare dissolved in 150 parts by volume of 2 N sulfuricacid. To this solution 500 parts of ice are added and the whole ispoured into the recently prepared diazonium salt solution. After 15minutes, 100 parts of crystallized soduim acetate are added to thecoupling suspension and the pH- value is adjusted to about 3 by means ofconcentrated sodium hydroxide solution. Stirring of the dyestuffsuspension is continued for 15 hours, the product of this process isfiltered off, and it is washed with 5000 parts by volume of water. Thedark filter cake gives after drying 38.5 parts of the dyestutf of theformula On polyester fibres with the dyestuff in finely dispersed form,intense reddish violet dyeings of excellent fastness to light andthermofixation are obtained.

EXAMPLE 2 16.3 parts of 2-cyano-4-uitro-anilene are dissolved at aboutC. in 50 parts by volume of concentrated sulfuric acid. 31 parts ofnitrosyl sulfuric acid of 41% 4 strength are added dropwise at 10-15 C.,and the batch is stirred for 1 hour at room temperature.

40.9 parts of a coupling component-obtained by condensation ofo-chloro-benzaldehyde and o-hydroxy-acetophenone in a strong alkalineand alcoholic medium and subsequent addition of S-amino-aceto-anilide onthe 0:, 3- unsaturated ketone thus formed-are dissolved in 40 parts byvolume of concentrated hydrochloric acid and 500 parts by volume ofwater. To this solution 500 parts of ice are added and then thediazonium sulfate solution is poured in. After 1 hour the pH-value ofthe coupling mixture is adjusted to about 4 by means of concentratedsodium hydroxide solution, and stirring of the dyestuif suspension iscontinued for 15 hours. Then the product of this process is filteredoff, washed with'5000 parts by volume of water and dried. There areobtained 54 parts of the dyestuff of the formula NH--CO-CH3 which isground and dispersed in the usual way. The dyestulf preparation thusobtained yields on polyester fibres bluish red dyeings of excellentfastness to light and to thermofixation.

EXAMPLE 3 18.3 parts of 2.4-dinitro-aniline are introduced into amixture consisting of parts by volume of glacial acetic acid and 20parts by volume of propionic acid, and diazotized at 1015 C. with 31parts nitrosyl sulfuric acid of 41% strength. After stirring for 1 hourthere remains a small excess of nitrous acid.

27.8 parts of a coupling component-obtained by condensation of acetoacetic acid ethyl ester with 3-aminopropionic acid anilide andsubsequent hydrogenation of the condensation product formed-aredissolved in parts by volume of glacial acetic acid. To this solutionthe solution of the diazonium acetate is added dropwise, the couplingmixture is stirred for 1 hour and the dyestuff solution is poured into amixture consisting of 1000 parts by volume of water and 1000 parts ofice, while stirring. The dyestufl? suspension is stirred for 15 hours,the product of this process is filtered off with suction, and washedwith 5000 parts by volume of water. After drying the filter cake, thereare obtained 42.5 parts of the dyestuff of the formula which afterdispersing on polyester yields clear reddish violet dyeings of excellentfastness to light and to thermofixation.

EXAMPLE 4 13.8 parts of 4-nitro-aniline are introduced into a mixtureconsisting of 100 parts by volume of glacial acetic acid and 20 parts byvolume of propionic acid, and diazotized at 10-15 C. with 31 parts ofnitrosyl-sulfuric acid of 41% strength.

32.6 parts of a coupling component-obtained by con- I this process isfiltered off, washed and dried. There are obtained 46 parts of thedyestuif of the formula which after dispersing in the usual manner givesa dyestuif preparation. Applied on polyamide fibres this preparationyields dyeings which are distinguished particularly in the manner thatat a good fastness to light they moreover possess an excellent fastnessto wet processing and to fixation.

In the following table further examples of dyestuffs of 4. Thewater-insoluble monoazo dyestuif of the formula NH- 0 O-UaHs 5. Thewater-insoluble monoazo dyestutf of the formula Formula 1 are indicated,which are obtained by diazotiz- 3 ing aromatic amines of Formula 2 andcoupling with E coupling components of Formula 3. The last column givesI the tint which is obtained when dyeing on polyester fibres. omg m No.Diazo component R1 Rz Ra Tint on polyester 2-chlord-4-nitro-aniline.MethyL. Red.

do henyl Do. ...do. Scarlet. 2,4-dini tro-anilinenfl do Violet.

9 .1 2-eyano-4-nitro-aniline do Do. 10 .do MethyL Do.

2-chloro-4-nitro-aniline Ethyl Scarlet.

2-cyano-4-nitro-aniline rdo Blu1sh 16d 2-chloro4-nitro-aniline heny Red.

2,4-dinitro-aniline-- do luish red. 16 2-cyano4-nitro-aniline do do dor.Do. 17 2-nitro-4-cyano-aniline .do do do Scarlet. 182-chloro-4-nitro-aniline MethyL. PIA-methylene dioxy-phenyl. o-Hydroxyphenyl. Do. 1 2-cyano-4-nitro-aniline. do d do Bluish red.

Z-chloroA-nitro-aniline 2-cyono-4-nitro-aniline 2-chloro-4-nitroan iline 24 2,4-dinitro-aniline .:do.:..

We claim: 1. A water-insoluble monazo dyestuft of the formula wherein Yis a hydrogen, chlorine or nitro group, R

is a methyl or phenyl group, R is a lower alkyl group,

and R is a methyl or lower alkoxy group.

2. The water-insoluble monoazo dyestuif of the formula 3. The waterinsoluble monoazo dyestuif of the formula 6. The Water-insoluble monoazodyestulf of the formula 111B- C O-@ 0115 References Cited UNITED STATESPATENTS JOSEPH P. BRUST, Primary Examiner C. F. WARREN, AssistantExaminer US. Cl. X.R. 84l, 50

